Water-insoluble dyestuffs of the monohalogeno-triazine-amino alkylene amino-azobenzene series



WATER-INSOLUBLE DYESTUFFS OF THE MONOHALOGENO-TRIAZINE-AMINO AL- KYLENEAMINO-AZOBENZENE SERIES Ronald Baker, Harry Rose Hadfield, Eric LeslieJohnson, and William Elliot Stephen, Manchester, England, assignors toImperial Chemical Industries Limited, London, England, a corporation ofGreat Britain No Drawing. Original application June 7, 1957, Ser. No.664,189. Divided and this application Apr. 9, 1959, Ser. No. 805,121

6 Claims. (Cl. 260-153) This invention relates to new azo dyestuffs andmore particularly it relates to new water-insoluble azo dyestuffsespecially useful for the dyeing of artificial textile fibres.

It has previously been proposed to manufacture azo dyestuffs containingone or more cyanuric nuclei by uniting azo dyestuffs containingappropriate groupings, either to each other, or to othercomplexes,'radicals or suitable residues by reaction with the halogen ofcyanuric halides.

When azo dyestuffs containing at least one triazine nucleus carrying atleast one halogen atom and which contain sulphonic acid or carboxylicacid groups are used for the dyeing of polyamide fibres such aspolyhexa: methylene adipamide, they dye the polyamide fibres incolourations which have good fastness to wet treatments, but which areuneven in depth of shade.

We have now prepared azo dyestuffs which are free fromwater-solubilising groups and which contain a monohalogenotriazinylaminoresidue attached to the residue of an aromatic azo compound containing aprimary, or secondary amino group through an alkylene chain, and we havefound that they may be used as dispersed dyestuffs for the dyeing ofpolyamide fibres to give colourations possessing excellent fastness towet treatments and which also have a satisfactory levelness of shade.

According to our invention therefore, there are provided the newwater-insoluble azo dyestuffs of the formula:

wherein R and R stand for hydrogen atoms or substituted or unsubstitutedhydrocarbon radicals and may be the same or different, X stands for ahalogen atom, Y

stands for a substituted or unsubstituted alkyl or aryl radical or for ahydroxyl or an amino group or for an organic radical containing anitrogen, oxygen orsulphur atom through which it is linked to the'triazine ring, Z stands for an alkylene radical and the benzene rings Pand Q may carry substitutents provided that R, R, Y, P and Q are freefrom sulpho, sulphato or carboxy groups.

As examples of hydrocarbon radicals represented by R and R there may bementioned alkyl such as methyl or ethyl, and aryl such as phenyl. Asexamples of substituents which may be present in the alkyl radicalsrepresented by R, R or by Y there may be'mentioned hydroxyl, alkoxy suchas methoxy, cyano and halogen such as fluorine and as examples ofsubstituents which may be present in the aryl radicals represented by R,R or by.

Y there may be mentioned alkyl such as methyl, alkoxyl such as methoxy,halogen such as chlorine or bromine. As examples of halogen representedby X in the above formula there may be mentionedjchlorine and bromine,

"ice

and as examples of the organic radicals containing a nitrogen, oxygen orsulphur atom and represented by Y in the above formula there may bementioned alkoxy such as methoxy and ethoxy, aryloxy such as phenoxy,substituted amino such as fl-hydroxyethylamino, methylarnino,dirnethylamino, phenylamino, cyclohexylamino, N-methylphenylamino,fl-cyanoethylamino and B-carbethoxyethylamino, and substituted mercaptosuch as methylmercapto.

As examples of the alkylene radicals represented by Z there may bementioned ethylene and propylene and as examples of the substituentswhich may be present in the benzene rings P and Q there may bementioned, alkyl such as methyl, alkoxy such as methoxy, halogen such aschlorine or bromine, nitro, cyano, alkylsulphonyl such asmethylsulphonyl, aminosulphonyl or substituted aminosulphonyl such as'methylaminosulphonyl, trifluoromethyl,

amino and acylamino such as acetylamino.

According to a further feature of the invention there is provided aprocess for the manufacture of the new water-insoluble azo dyestuffs, ashereinbefore defined,

which comprises reacting an azo compound of the formula I wherein P, Q,R, R and Z have the meanings stated above with one molecular proportionof a triazine of the formula:

wherein X and Y have the meanings stated above.

As examples of triazines which may be used in this process of theinvention there may be mentioned 2:4-dichloro-fi-phenoxy-l :35-triazine, 2 4-dichloro-6-methoxy- 1:3:5-triazine, 2:4-dichloro 6dimethylamino-l :3 :S-triazine, 2 4-dichloro-6-phenylamino-1 :3S-triazine, 2 4-dichloro-6-j8-cyanoethylamino-l :3 S-triazine, 24-dichloro- 6-phenyl-1 3 S-triazine, and 2 4-dichloro-6-methyl-1 3 5-triazine.

As examples of azo compounds of the Formula I which may be used in theabove process there may be mentioned 2'chloro-4-nitro-4-(N-B-hydroxyethyl-N-fi-aminoethyl) aminobenzene,2-chloro-4-ethanesulphonyl 4 (N-flhydroxyethylamino) -ethylaminoazobenzene.

carbonate or sodium bicarbonate The products usually separate asinsoluble solids 'from the reaction medium,

but, if necessary, may be precipitated by adding water to the reactionmedium. They may then be isolated by filtration. It is preferred to drythe products at a relatively low temperature for example between 40 C.and

The azo compounds of the Formula I used in this process of the inventionmay be obtained by diazotising an amine of the formula:

and coupling the diazo compound so obtained with a coupling component ofthe formula:

i i" Q -z-NH (Formulall) wherein P, Q, R, R and Z have the meaningsstated above.

According to a further feature of the invention there is provided analternative process for the manufacture of the new water-insoluble azodyestuffs as h'ereinbefore defined which comprises diazotising anaromatic amine of the formula:

and coupling the diazo compound so obtained with a coupling component ofthe formula:

r @tatc a...

C i I x wherein P, Q, R, R, X, Y and Z have the meanings stated above.

As examples of aromatic amines which may be used in this alternativeprocess of the invention there may be mentioned 2-chloro-4-nitroaniline,2-chloro-4-ethanesulphonylaniline, 4 cya'no 2 trifluorom'ethylanilineand 6-chloro-2 4-dinitroaniline'.

The coupling components used in this alternative process may be obtainedby interacting a triazine as hereinbefore defined with a couplingcomponent of Formula II. As examples of such coupling components ofFormula II there may be mentioned N-ethyl-N-(fi-aminoethyl)aniline,N-(B-hydroxyethyl) N (,3 aminoethyl) aniline andN-B-hydroxyethyl-N-[B-(fl-hydroxyethylamino) -ethyl] aniline.

This alternative process of the invention may be conveniently broughtabout by dissolving or suspending the aromatic amine in an aqueoussolution of hydrochloric acid, adding sodium nitrite, adding the diazosolution or suspension so obtained to a solution of the couplingcomponent in a dilute aqueous solution of hydrochloric acid, addingsodium acetate until the mixture is no longer acid to Congo red andfiltering err the dyestufi which is precipitated.

According to a further feature of the invention there is provided amodified process for the manufacture of the new water-insoluble azodyestuffs, as hereinbefore defined, wherein Y stands for a hydroxyl oran amino group or for an organic radical containing a nitrogen, oxygenor sulphur atom through which it is linked to the triazine ring whichcomprises treating an azo compound of the formula:

(Formula III) wherein P, Q, R, R, X and Z have the meanings stated abovewith a compound of the formula: H -Y wherein Y stands for a hydroxyl oran amino group or for an organic radical containing a nitrogen, oxygenor sulphur atom through which it is linked to the hydrogen atom. Asexamples of such organic radicals there may be mentioned methoxy,phenoxy, thiophenoxy, methylamino, di- (fl-hydroxyethyl) amino,ethylamino and fl hydr'ox'yethylamino.

The above azo compounds of Formula IH may be ob= tained by reaction of acyanuric halide with an azo compound of Formula I.

This modified process of the invention may be con veuiently broughtabout by heating the azo compound of Formula III and the compound of theformulai HY together in a suitable solvent, for example acetone, and inthe presence of an acid-binding agent, and filtering off the azodyestutf which is precipitated. If desired water may be added at thecompletion of the reaction to ensure complete precipitation of all theazo dyestutf.

For their use in dyeing, the new water-insoluble azo dyestuffs of theinvention may be dispersed in aqueous medium by known methods forexample by gravel milling with the aid of dispersiiig agents for examplethe sodium salt of methylenedinaphthalene sulphonic acid and, ifdesired, buffering agents may be added to the dispersions to maintainthe pH within a range of 6 to 8 to keep to a minimum the removal byhydrolysis of halogen atoms from the triazine nucleus.

The new water-insoluble azo dyestuffs of our invention may be appliedfrom aqueous dispersion either by printing or dyeing methods to animalfibres such as wool and silk and to cellulose esters such as celluloseacetate and cellulose triace'tate and they are particularly useful forapplication to synthetic fibres for example polyamide fibres such aspolyhexamethyleue adipamide and the polymer of the invention containdiazotisable primary amino groups they may be applied to one of thetextile fibres described and then diazotised on the fibre and coupledwith a suitable coupling component, for example 2-hydroxy-3-naphthoicacid. In this way valuable shades, for

example navy blues and blacks may be obtained.

The invention is illustrated but not limited by the following examplesin which parts and percentages are by weight:

EXAMPLE 1 55.8 parts of2-chloro-4-ethylsulphonyl-4-N-,3-hydroxyethy1-N-fi-(4:6-dichloro l :3:5-triazin 2 ylamino)-ethylaminoazobenzen'e are stirred with 280 partsof water and 54 parts of 7.5% aqueous sodium hydroxide solution. Themixture is heated to C. and stirred at this temperature for 12 hours.The mixture is cooled and made slightly acid to Congo red paper byaddition of sulphuric acid. The product is filtered off, washed anddried.

The product is 2-chloro-4-ethylsulphonyl-4'-N-p-hydroxyethyl N 13(4-chloro-6-hydroxy-l:3z5-triazin-2- ylamino)-ethylaminoazobenzene. Itdyes cellulose acetate rayon and nylon from finely-divided aqueousdispersions in orange shades of good fastness to washing.

EXAMPLE 2 55.8 parts of the azo compound used in Example 1 are stirredwith 450 parts of acetone and 12.2 parts of monoethanolamine are added.The mixture is heated and stirred at a tmpeiature of 40 C. for an hour,then cooled to 20 C. and 450 parts of water are added slowly. Theprecipitated product is then filtered off, washed with water and dried.v

The product obtained is 2-chloro-4-ethylsulphonyl-4'- N Bhydroxye'thyl-N-B-(4-chlor0-6-5-hydroxyethylamino-lz3z5-triazin 2ylamino)ethylaminoazobenzene. It dyes cellulose acetate rayon and nylonfrom finely-divided aqueous dispersions in orange shades of goodfastness to washing.

EXAMPLE 3 A solution of 69 parts of sodium nitrite in 50 parts of wateris added slowly at 10 C. to a stirred solution of 21.95 parts of2-chloro-4-ethylsulphonylaniline and 25 parts of 36% aqueoushydrochloric acid in parts of acetic acid. After standing for 10 minutes100 parts of water are added and the solution of the diazonium compoundso obtained is added, ata temperature below 10 6., to a stirred solutionin 400 parts of acetone of 32.35 parts of the compound obtained byreacting together equimolecular amounts of 2:4-dichloro-6-methoxy-l :3S-triazine and N-( B-hydroxyethyl-N fi-aminoethyl)aniline in acetone inthe presence of sodium bicarbonate. A solution of 6.15 parts ofanhydrous sodium acetate in 75 parts of water is then added and themixture is stirred for 24 hours. The mixture is then filtered and theproduct is washed with Water and dried at a temperature between 40 C.and 50 C. The product so obtained dyes nylon from a finely dispersedaqueous suspension to give orange shades of good fastness to washing.

The following table contains further examples of dyestuifs of theinvention which may be obtained by coupling a diazotised aromatic amineas hereinbefore defined with a coupling component as hereinbeforedefined.

The coupling components mentioned in the above table may be obtained bythe following methods:

N -fl (4-ch lr0-6-fi-hydr0xyethy lamina-1 :3 -triazin-2- ylamino)-ethyl-N-ethylaniline A solution of 18.45 parts of cyanuric chloride in125 parts of acetone is added to 150 parts of water at 0 C. To theslurry so obtained is added 16.4 parts of Nethyl- N-fl-aminoethylanilinedissolved in 125 parts of acetone keeping the temperature below C. 10%sodium carbonate solution in water is added simultaneously to maintainneutrality. The insoluble N-B-(4:6-dichloro- 1 3 5-triazin-2-ylamino)-ethyl-N-ethylaniline is filtered ofi and washed with water. 31.2 partsof the dried product are stirred with 200 parts of acetone and 12.2parts of monoethanolamine is added. The mixture is heated at 45 C. for 1hour. To the cooled mixture is then added 600 parts of cold water toprecipitate the product. After stirring 1 hour the product is filteredoif, washed until alkali free with water and dried. The N-B-(4- chloro 6p3 hydroxyethylamino 1:3:5 triazin 2- ylamino)-ethyl-N-ethylaniline soobtained is a white solid, melting at a temperature between 178 C. and179 C.

N -;9- (4-chloro-6-fl-hydr0xyethylamino-I :3:5 -triazin-2- ylamino)-ethyl-N-/3-hydroxyethylaniline If in the above process 18 parts ofN-B-hydroxyethyl- N-;8'-aminoethyl aniline are used in place of N-ethyl-N-fl-aminoethylaniline the product obtained is N-fl-(4- chloro 6 3hydroxyethylamino 1:3:5 triazin 2- ylamino) ethyl N phydroxyethylaniline, melting at 140 C.

N -}3-(4-ch l0r0-6-N -methylgl ucamyI-I :3 :5 -triazin-2- ylamino)-ethyl-N-ethylaniline 31.2 parts of N ,8 (4:6 dichloro -1:3:5 triazin 2-ylamino)-ethyl-N-ethylaniline, 19.5 parts of N-methylglucamine and 8.4parts of sodium bicarbonate are stirred with a mixture of 165 parts ofacetone and parts of water. The mixture is heated at a temperaturebetween 45 C. and 50 C. for 1 /2 hours. After cooling to 20 C. theproduct is filtered off, washed with cold water and dried. The compoundso obtained is N-B-[4-chloro-6- N methylglucamyl 1:3:5 triazin 2ylamino] ethyl- N-ethylaniline, melting at a temperature between 176 C.and 177 C.

This application is a divisional application of our copendingapplication Serial No. 664,189, which was filed in the United StatesPatent Office on June 7, 1957.

What we claim is:

1. Water-insoluble dyestuffs of the formula:

R is selected from the group consisting of (a) lower alkyl, and loweralkyl substituted by a member selected from the class consisting ofhydroxy, lower alkoxy, cyano, and fluorine, and (b) phenyl, and phenylsubstituted by a member selected from the group consisting of loweralkyl, lower alkoxy, chlorine, and bromine; R is selected from the classconsisting of hydrogen and B-hydroxyethyl; Z is lower alkylene; X isselected from the group consisting of bromine and chlorine atoms; Y isselected from the class consisting of (a) the aliphatic radicals: loweralkyl, lower alkoxy,

lower alkylamino, di-lower alkylamino, cyclohexylamino,fl-hydroxyethylamino, di-(fi-hydroxyethyDamino, fi-cyanoethylamino,hydroxyl and amino; and (b) the aromatic radicals: phenyl, phenoxy,phenylamino and thiophenoxy, wherein the phenyl rings carry substituentsselected from the group consisting of hydrogen, lower alkyl, loweralkoxy, chloro, and bromo;

6. 2-chloro-4-ethylsulfonyl 4'-N- 8hydroxyethyl-N- 3- (4 chloro 6hydroxy 1:3:5 triazin 2 ylamino)- ethylaminoazobenzene.

References Cited in the file of this patent UNITED STATES PATENTS2,873,269 Fasciati et al. Feb. 10, 1959

1. WATER-INSOLUBLE DYESTUFFS OF THE FORMULA: